In the present work, coordination possibilities of the system dapdoH(2)/Ni2+, being dapdoH(2)=2,6-diacetylpyridine dioxime, have been explored, offering as a result a number of unprecedented clusters with a variety of topologies and magnetic behaviors. Depending on the precursors and reaction conditions, several compounds named [Ni-2(dapdO)(2)] (1), [Ni-3(OH)(BzO)(3)(dapdo)(dapdoH(2))(H2O)]center dot 1.25H(2)O (2), [Ni-3(AcO)(4)(dapdoH)(2)(H2O)(2)]center dot H2O (3), and [Ni-4(ACO)(3)(dapdo)(dapdoH)(2)(H2O)(3)]center dot(AcO)center dot 3H(2)O (4) were achieved and structurally well-characterized. Dc magnetic measurements were carried out in the 2-300 K range revealing antiferromagnetic interactions for (2-4) compounds and diamagnetic response for the square planar coordinated complex (1).